Certain pyrimidine-containing dyestuffs

ABSTRACT

New dyes of the formula:   IN WHICH TWO OF THE GROUPS X are hydroxyl and the third X is unsubstituted or substituted alkylamino, unsubstituted or substituted phenylamino, phenylthio, aliphatic, cycloaliphatic or aromatic acylamino or N&#39;&#39;-alkylureido for dyeing synthetic material. Dyeings obtained therewith have good fastness properties. The invention relates to new dyes based on anthrapyrimidines for synthetic fibers.

ilnite Patent 1 1 Eilingsield et al.

[ CERTAIN PYRlMlDlNE-CONTAINING DYESTUFFS {75] Inventors: HeinzEiiingsfeld, Frankcnthul; Gerd Schwantje, Ludwigshafen. both of Germany[73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft,Ludwigshafen/ (Rhine), Germany [22] Filed: May 10, 1972 [2]] App]. No:252,031

[52] U.S. Cl 260/2565 R, 260/40, 260/247.l, 260/251 A, 260/256.4 Q [5 1]int. Cl C07d 51/46 [58] Field of Search... 260/256.5 R, 256.4 Q, 247.],260/2472, 25! A [56] References Cited FOREIGN PATENTS OR APPLICATIONSl,l59 456 l2/l963 Germany 260/25! Primary Exuminer-Richard J. GallagherAttorney, Agent, 0'' FirmJohnston, Keil, Thompson & Shurtleff Jan. 28,1975 [57] ABSTRACT New dyes of the formula:

8 Claims, No Drawings in which two of the radicals X are hydroxyl andthe third X is alkylamino of one to eight carbon atoms in which one ortwo hydrogen atoms may be replaced by hydroxyl, alkoxy of one to threecarbon atoms, cyano, carboxamido, alkoxycarbonyl of a total of two tofive carbon atoms, sulfonamido or pyrrolidon-Z-yl-l, phenylamino inwhich one or two hydrogen atoms may be replaced by chlorine, bromine,hydroxy, trifluoromethyl, nitro, sulfonamido, carbamoyl, alkoxycarbonylof a total of two to five carbon atoms, methyl, ethyl and/or methoxy orethoxy, phenylthio, aliphatic acylamino of two to six carbon atoms inthe acyl moiety in which one or two hydrogen atoms may be replaced bychlorine, bromine, methyl, ethyl, methoxy or ethoxy, cycloaliphaticacylamino of seven to eight carbon atoms in the acyl moiety,benzoylamino in which one or two hydrogen atoms may be replaced bychlorine, bromine, methyl, ethyl, methoxy and/or ethoxy, or N'- allylureido of two to five carbon atoms in the alkyl moiety.

The new dyes dye synthetic fibrous material of linear aromaticpolyesters and cellulose acetate deep blue to red violet shades byconventional dyeing methods. The dyeings have good to outstandingfastness properties.

The unsubstituted or substituted alkylamino groups represented by X maybe those of one to eight carbon atoms in the alkyl moiety, for examplemethylamino, ethylamino, n-propylamino, n-butylamino,,B-carbonylmethoxyethylamino, B-carbonylethoxyethylamino,B-carbonylbutoxyethylamino, B-carbonyl-B-hydroxyethoxyethylamino,B-carbonyl-B-chloroethoxyethylamino, B-carbonylaminoethylamino,B-(carbonyl- N,N-dimethylamino)-ethylamino,B-(N,N-dimethylsulfonamido-ethylamino, B-sulfonamidoethylamino,B-cyanoethylamino, B-hydroxyethylamino, B-methoxyethylamino,fl-ethoxyethylamino, -nbutoxyethylamino and B-(pyrrolidon-Z-yl-lethylamino.

Examples of substituted phenylamino groups are: 2-

chlorophenylamino, 3-chlorophenylamino, 4- chlorophenylamino,Z-methylphenylamino, 3- methylphenylamino, 4-methylphenylamino, 2-methoxyphenylamino, 3-methoxyphenylamino, 4- methoxyphenylamino,2-ethoxyphenylamino, 3- ethoxyphenylamino, 4-ethoxyphenylamino, 2-hydroxyphenylamino, 3-hydroxyphenylamino, 4-

hydroxyphenylamino, 2,4-dichlorophenylamino, 3,4- dichlorophenylamino,2-methyl-4-chlorophenylamino, 4-chloro-2-methylphenylamino, 4-chloro-2-methoxyphenylamino, 4-methoxy-2- chlorophenylamino,2,4-dimethoxyphenylamino, 4-(B- hydroxyethyl)-phenylamino, 3-trifluoromethylphenylamino, 3-

sulfonamidophenylamino, 3-(y-methoxypropylaminosulfonamido)-phenylamino,3-(N '-(B methoxy)-ethylsulfonamido)-phenylamino, 3-(morpholinosulfonyl)-phenylamino, 3-(N-isobutylsulfonamido)-phenylamino, 3-(N'-(y-ethoxy)-propylsulfonamido)-phenylamino, 3-(N- ethylsulfonamido)-phenylamino, 3-methoxycarbonylphenylamino, 3-

ethoxycarbonylphenylamino, 3-(N-methylcarboxamido)-phenylamino,3-(N,N'-dimethylcarboxamido)- phenylamino, 3-(N-n-butylcarboxamido)-phenylamino, 3-nitro-4-methylphenylamino, 3-(N-methylsulfonamido)-phenylamino, 3-(N propylsulfonamido)-phenylamino,3-(N-nbutylsulfonamido)-phenylamino, 3-(N'-isobutylsulfonamido)-phenylamino, 3-(N'-(y-methyl)butylsulfonamido)-phenylamino, 3-(N'-(B,B-dimethyl-'y-hydroxy)-propylsulfonamido)-phenylamino, 3-(N-methyl-N-(,8-hydroxyethyl)-sulfonamido)- phenylamino,3-(N,N'-diethylsulfonamido)- phenylamino, 3-(piperidinosulfonamido)-phenylamino, 3-(pyrrolidinosulfonamido)- phenylamino,3-(N'-ethylcarboxamido)-phenylamino,3-(N'-n-propylcarboxamido)-phenylamino,3-(N'-(yethoxy)-propylcarboxamido)-phenylamino, 3-(N-cyclohexylcarboxamido)-phenylamino, 3-(N',N'-diethylcarboxamido)-phenylamino, 3-(N'-piperidinocarboxamido)-phenylamino or 3-((B-ethoxy)-ethoxycarbonyl)-phenylarnino.

Examples of unsubstituted or substituted acylamino for X are:acetylamino, propionylamino, nbutyrylamino, isobutyrylamino,chloroacetamino, bromoacetamino, B-chloropropionylamino,a-chloropropionylamino, B-bromopropionylamino, phenoxyacetamino,dichloroacetamino, B-chlorobutyrylamino, a-ethylcapronylamino,,B-methoxypropionylamino, 'y-phenoxybutyrylamino, hexahydrobenzoylamino,benzoylamino, Z-chlorobenzoylamino, 3- chlorobenzoylamino,4-chlorobenzoylamino, 2- methoxybenzoylamino, 3-methoxybenzoylamino, 4-methoxybenzoylamino, 3-bromobenzoylamino, 4- bromobenzoylamino,2-methylbenzoylamino, 3- methylbenzoylamino or 4-methylbenzoylamino.

Examples of N-alkylureido groups for X are N- butylureido,N,N'-dimethylureido, N'-'ymethoxypropylureido and N,N'-diethylureido.

Because of their tinctorial behavior, dyes of the formula (Ia) arepreferred:

X 0 OH in which one X is hydroxyl and the other X is phenylamino and thetwo hydrogen atoms in the phenyl may be replaced by chlorine, bromine,trifluoromethyl, nitro, methyl, ethyl, methoxy, ethoxy, sulfonamido,carbamoyl, or alkoxycarbonyl of two to five carbon atoms.

Because of their outstanding fastness to light and dryheat pleating andsetting, dyes of the formula (la) are especially preferred in which oneX is hydroxyl and the other X is 3-sulfonamidophenylamino of the formula(V in which R is hydrogen or alkyl of one to eight carbon atoms and R isalkyl of one to eight carbon atoms and the alkyls may bear methoxy,ethoxy, propoxy or butoxy as a substituent or the group is a saturatedfive-membered or six-membered heterocyclic ring.

Dyes of the formula (Ia) have quite particular preference in which one Xis hydroxyl and the other X is 3- sulfonamidophenyl of the formula:

-N SO R in which R is hydrogen or alkyl of one to eight carbon atoms andR is alkoxyalkyl of three to eight carbon atoms or the group ispiperidino, pyrrolidino or morpholino.

The new compounds of the formula (I) are prepared for example by themethod described in German Pat. No. 1,159,456 from a substitutedformamidine of the general formula (II):

in which X has the above meanings, R and R are identical or differentlower alkyls such as methyl, ethyl, propyl or butyl and A is a halogenanion, by the action of an ammonium salt of a weak acid in a solvent.Those solvents which dissolve salts of nitrogenous bases such as glycol,diglycol, propylene glycol, glycol monoalkyl ethers such as glycolmonomethyl, monoethyl or monobutyl ethers of N-methylpyrrolidone areparticularly suitable.

Examples of suitable ammonium salts of weak acids are ammonium formate,ammonium acetate and ammonium carbonate.

Cyclization of compounds (11) is carried out by stirring a suspension inthe said solvents at from to 150C, preferably at from 70 to 120C.

The formamidine derivatives of formula (11) are obtained by a knownmethod from an a-aminoanthraquinone derivative of the general formula([11):-

x o NH2 (III) in which X has the above meanings, and aN,N-dialkylformamide halide at from 20 to C. The formamide halide may beadded direct, but is more advantageously prepared in situ in thepresence of the aminoanthraquinone (111) from a N,N-dialkylformamide anda chlorinating agent such as thionyl chloride or phosphorus trichloride.Conversion to (II) takes place at the same time. Reaction to form theformamidine derivative (11) advantageously takes place in an inertsolvent such as benzene, toluene, xylene, chlorobenzene ordichlorobenzene at a temperature of from 20 to 100C.

The reactants (the B-aminoanthraquinone derivative (III) and theformamide halide) are conveniently used in the molar ratio 1 1.1 to l2.5. This is also true when the formamide halide is prepared in situ forexample from N,N-dimethylformamide and thionyl chloride or phosphorustrichloride in the reaction mixture.

The following are examples of suitable a-aminoanthraquinone derivitivesof the formula (III):

l,5-dihydroxy-4-propionylaminc-8- aminoanthraquinone,l,8-dihydroxy-4-(B-carbethoxyethylamino )-5- aminoanthraquinone,1,5-dihydroxy-4acetamino-8-aminoanthraquinone,l,5-dihydroxy-4-chloroacetamino-S- aminoanthraquinone,l,5-dihydroxy-4-(B-chloropropionylamino )-8- aminoanthraquinone,l,5-dihydroxy-4-(n-butyrylamino)-8- aminoanthraquinone,1,5-dihydroxy-4-(isobutyrylamino )-8- aminoanthraquinone,l,5-dihydroxy-4-tetrahydrobenzoylamino-8- aminoanthraquinone,l,5-dihydroxy-B-hydroxyethylamino-8- aminoanthraquinone,1,5-dihydroxy-4-(,B-methoxyethylamino)-8- aminoanthraquinone,l,5-dihydroxy-4-(B-carboethoxyethylamino)-8- aminoanthraquinone,1,5-dihydroxy-4-(B-cyanoethylamino)-8- aminoanthraquinone,l,5-dihydroxy-4-B-(pyrrolidon-2-yl-1)-ethylamino-8- aminoanthraquinone,

1,5 -dihydroxy-4-anilino-8-aminoanthraquinone,

aminoanthraquinone, 1,5-dihydroxy-4-(2'-anisidino)-8-aminoanthraquinone,

1,5-dihydroxy-4-(2 '-methylamilino)-8- aminoanthraquinone,

l,5-dihydroxy-4-( 3 '-methylphenylamino)-8- aminoanthraquinone,l,5-dihydroxy-4-(4-methylanilino)-8- aminoanthraquinone,

once of oxidizing agents such as nitrobenzene, m-nitrobenzenesulfonicacid or alkali metal salts of the same, chloroanil or dimethylsulfoxide.The reaction is cooled to room temperature, suction filtered, washedwith methanol and water and dried. The dye obtained has the formula:

conveniently carried out at a temperature of from 140 HO to 200C,preferably at from 160 to 175C. The form- 5 amide serves at the sametime as a solvent. Some of the formamide may also be replaced by anotherhigh boiling inert solvent such as nitrobenzene, NH O OHdichlorobenzene, trichlorobenzene, dimethylforml amide orN-methylpyrrolidone.

The amolfm of Oxldlzmg agent generally from to It dyes polyesters fullred shades. The yield is 18.2 parts 30% by weight, preferably from to20% by weight, of a dark brown d pow er.

based on the formamide used. The amount of formamide is generally fromtwice to ten times the weight EXAMPLE 2 of the anthraquinone derivative(IV). When a neutral 25.2 parts of 1,8-dihydroxy-4-(B- solvent is used,the amount of formamide may bedecarbethoxyethylamino)-5-aminoanthraquinone is creased to 0.5 to twi eth weight f (IV), stirred into a mixture of 250 parts of toluene and 9.5

The reaction is generally completed after from 4 to partsofdimethylformamide. 10.7 parts of thionyl chlo- 10 hours. Thereaction mixture is worked up by pour- F pp at room tempercetufe and eWhole ing it into water, suction filtering the precipitate and heatedfor h h 2 hours at 70 After eoohhg, h Washing it well When an inertSolvent Which is not whole is suction filtered and the residue 18 washedwith cible with water has been used, the solvent is distilled acetone iOff with Steam after pouring into water and the dye is The residue whilestill moist with acetone 15 introisolated from the aqueous residue, forexample by filduced at F temperature mm a mlxture of 25 parts nation. ofammonium formate and 2 50 parts of ethylene glycol The Same dyes areobtained by this method as by that monomethyl ether. After stirring for1 hour at room mentioned previously temperature the whole is heated for3 hours at 70C.

The new dyes are suitable for dyeing linear poleysters After coolmg toroom temperature whole is suction and cellulose acetate. The derivativesof 1,5-dihydroxyfiltered and product washed wlth methanol and 8 10amhrapyrimidine of 5 y y water and dried. 23.4 parts of the dye of theformula: anthrapyrimidine and mixtures of the same are particu- 9 larlysuitable. H C O-C-H C-H C-NH 5 2 2 2 The following Examples illustratethe invention. The parts specified are parts by weight.

EXAMPLE 1 I 19.5 parts of l,5-dihydroxy-4-propionylamino-8-aminoanthraquinone is stirred into a mixture of 240 15 Obtalhed-h ye Pey fullbhle Shadesparts of chlorobenzene and 9.2 parts of dimethylform-40 T ye ldehhfled the fellewlhg Table y the amide. 10.7 parts of thionylchloride is dripped in at Stltuehts the formula; room temperature andthe whole is then heated for 2 Z hours at C. Suction filtration iscarried out at room temperature and the residue is washed with acetone.The residue still moist with acetone is introduced into 45 a mixture of30 parts of ammonium acetate and 250 parts of ethylene glycol monomethylether at room Y 0 OH temperature, stirred for 1 hour at room temperatureare obtained by a method analogous to that described and heated for 4hours at C. The whole is then 11 Example 1:

Example Y Z Shade of dyeing on linear polyester 5 HNOCCH -OH red violet4 HNOCCH Cl -OH red violet 5 -HNOCCH CH Cl -OH red Violet 6 -HNOCCH CHCH -OH red violet 7 -HNOCCH CH 5 -OH red violet 8 -HNOC-@ -0H r'edviolet;

9 -OH -HNOCCH O- red violet 10 -OH red violet -HNOC Continued Shade fExample Y Z dyeing on linear polyester 11 OH HNOCQOCPLS I'ed violet 12OH -HNOC-Q bed violet 13 OH NHCONH-(CH2)3CH3 red violet 1 1 -HNCH2CH2OHOH blue 15 -HNCH2CH2OCH3 OH blue 16 -NHCH2CH2CO2C2H5 OH blue 17 OH-NHCH2CH2CONH2 blue 18 -HNCH2CHCN -o11 blue 19 -HNcH cH -N;:] -on bluec1-1 20 OH HNCH2CH2SO2N\ blue 011 21 41110001101 7 OH red violet 22-HNOCCH CH CH Cl OH red violet 25 OH -HNOCCH(C2I-I5)(CH2)3CH5 red violet2 1 -HNOCCH2CH2OCH5 OH red violet 25 OH -HNOCCH2CH2CH2O red violet 26-HNOCN(CH3)2 -o11 red violet 27 -I-INOCN(C2H5)2 OH red violet 28-HNOCNHCH2CH2CH2OCH -o11 red violet 29 HNOCNHCH2CH2 OH r'ed violet 3oHNCH2CH2CH2CH5 -OH blue 51 OH -HNCH2CH2OC2H5 blue 2-HNCH2CH2OCH2CH2CH2CH3 011 blue 53 -HNCH2CH2CO2CH2CH2CH2CH3 OH blue OH-HNCH2CH2CO2CH2CH2OH blue OH -HNCH2CH2CO2CH2CH2C1 blue c11 6-HNCH2CH2CO21\\ OH blue 57 -HNCH2CH2SO2NH2 OH blue 11 12 EXAMPLE38 100C,cooled to room temperature, suction filtered, 25 parts f 1y5 dihydmxy 4anilino 8 washed withmethanol and water and dried. The dyeaminoamhraquinone is Stirred into a mixture f 250 mixture obtained whichconsists of the dyes of the forparts oftoluene and 11 partsofdimethylformamide. l3 mulae? no \N a COQNH and H3CO- OH parts ofthionyl chloride is dripped in at room tempera- 15 dyes polyesters fullblue green shades. The yield is 17.4 ture and then the whole is heatedfor 2 hours at 70C. parts of a blue powder. Suction filtration iscarried out at room temperature I and the residue is washed withacetone.

The residue, while still moist with acetone, is introduced into amixture of 25 parts of ammonium formate EXAMPLE 4() and 250 parts ofethylene glycol monomethyl ether at room temperature. After having beenstirred for 1 hour at room temperature the whole is heated for 3 hoursat 100C, cooled to room temperature, suction filtered, 15.4 parts of amixture of about equal parts of 1,5-

washed with methanol and water and dried. The dyedihydroxy-4(3-sulfonamidoanilin o)-8- obtained has the formula:aminoanthraquinone and 1,8-dihydroxy-4-(3- HO WNsulfonamidoanilmo)-5-aminoanthraquinone 1S stirred into a mixture of 125parts of toluene and 5.3 parts of dimethylformamide. 6.7 parts ofthionyl chloride is dripped in at room temperature and then the whole isheated for 2 hours at 70C. Suction filtration is carried OH out at roomtemperature and the residue is washed with acetone.

The residue while still moist with acetone is introand dyes polyestersfull blue shades. The yield is 20.2 duced at room temperature into amixture of 12.5 parts parts of a dark blue powder. of ammonium formateand 125 parts of ethylene glycol monomethyl ether, stirred for 1 hour atroom tempera- EXAMPLE 39 ture, heated for 3 hours at 100C, cooled toroom tem- 22.6 parts of a mixture of about equal parts of 1,5- perature,suction filtered, washed with methanol anddihydroxy-4-(4-anisidino)-8-aminoanthraquinone and 0 wiiitef and dried-The y mixture Obtained, Which1,8-dihydroxy-4-(4'-anisidino)-5-aminoanthraquinone talHS the dy s 0fthe mulae! is stirred into a mixture of 210 parts of xylene and 9.2 dyespolyesters full blue shades. The yield is 14.9 parts. parts ofdimethylformamide. 10.7 parts of thionyl chloride is dripped in at roomtemperature and the whole is then heated for 2 hours at 70C. Suctionfiltration is carried out at room temperature and the residue is EXAMPLE41 washed with acetone.

The residue while still moist with acetone is introduced at roomtemperature into a mixture of 25 parts of ammonium formate and 250 partsof ethylene glycol 27.5 parts of 1,8-dihydroxy-4-(3'-chloroanilino)-5-monomethyl ether. After the whole has been stirred foraminoanthraquinone is stirred into a mixture of 250 1 hour at roomtemperature it is heated for 3 hours at 65 parts of toluene and 1 1parts of dimethylformamide. 13

O O OH 13 14 parts of thionyl chloride is dripped in at room tempera- NHture and then the whole is heated for 2 hours at 70C.

Suction filtration is carried out at room temperature and the residue iswashed with acetone. C1

The residue while still moist with acetone is intro- 5 duced at roomtemperature into a mixture of 25 parts HO O OH of ammonium formate and250 parts ofethylene glycol monoethyl ether, stirred for 1 hour at roomtemperais obtained; it dyes polyesters full blue shades.

ture, heate f 3 hOurS at COOIed t0 room The dyes set out in thefollowing Table are obtained perature, suction filtered, washed withmethanol and 10 by a th d analogo s to that described in Example waterand dried. 23.1 parts of the dye of the formula: 41;

z u A Y O OH Shade on Example Y Z polyester,

#2 -HN -OH I blu 43 -HN CH -OH l 4 -OH blue 5 OH -HN O blue 46 -OH -HNblue CH CH OH O -OH blue Cl -OH blue n -OH blue 50 -OH JUVUOCHB blue 5 lo blue OCH Continued Shade on Example Y Z polyester OH blue green 1-1 OHblue green H CO I OCH 5 OH HN so uu blue 55 OH S blue violet CO CH OHblue 57 OH -HN CONH(CH cn blue 58 OH HN\/CF5 blue 59 OH -HN1i ;[NO blueEXAMPLE 60 tered, washed with methanol and water and dried. The

21.6 parts of1,4-dihydroxy-5amino-8-(B-chloropropionylamino)-anthraquinone is stirredinto a mixture of 250 parts of toluene and 9.2 parts ofdimethylformamide. 10.7 parts of thionyl chloride is dripped in at roomtemperature and the whole is then heated for 2 hours at C. Suctionfiltration is carried out at room temperature and the residue is washedwith acetone.

The residue is introduced while still moist with acetone into a mixtureof 25 parts of ammonium formate and 250 parts of ethylene glycolmonomethyl ether, stirred for 1 hour at room temperature, heated for 3hours at 70C, cooled to room temperature, suction fil- 4O dye of theformula:

obtained dyes polyesters full red shades. The yield is 17.9 parts.

The dyes set out in the following Table are obtained by a methodanalogous to that described in the preceding Example:

OH O X Example X Shade on polyester 61 HNOCCH red violet 62 -HNOCCH Clred violet 63 -HNOCCH CH CH red violet 6 HNCOCH cu 3 red violet 2 \CHContinued Example X Shade on polyester 65 -HNCOCH O- red violet 66 -HNCOred violet 67 -HNCO-OCH red violet 68 -I-INCONH-(CI-I CH red violetEXAMPLE 69 EXAMPLE 71 parts of a mixture of about equal parts of 1,5-dihydroxy-4-(4-chloroani1ino)-8-;aminoanthraquinone 10 parts ofl,S-dihydroxy-4-anilino-8- and l,8-dihydroxy-4-(4-chloroanilino)-5-aminoanthraquinone, 50 parts of formamide and 2.5 parts of nitrobenzeneare heated for 6 hours at 175C, cooled to room temperature and pouredinto ice-water. The precipitate is suction filtered, washed with waterand dried. The isolated product contains the dye of the formula:

O OH

and dyes polyesters full blue shades. The yield is 9.6 parts.

EXAMPLE 70 is obtained which dyes polyesters full blue shades.

aminoanthraquinone, 50 parts of formamide and 1 part ofdimethylsulfoxide are heated for 5 hours at C, cooled to roomtemperature and poured into ice-water. The precipitate is suctionfiltered, washed with water and dried. 8.7 parts of a mixture continingthe dyes of the formulae:

ClQN H W and OHO

in about equal parts is obtained. The mixture dyes polyesters full blueshades.

EXAMPLE 72 and dyes polyesters full blue shades. The yield is l0.3parts.

EXAMPLE 73 10 parts of a mixture of about equal parts of 1,5-dihydroxy-4-(3-(N-methylsulfonamido)-anilino)-8- aminoanthraquinone and1,8-dihydroxy-4-(3-(N- 3,862,944 19 20methylsulfonamido)-anilino)--aminoanthraquinone, 50 parts of formamideand 4 parts of sodium mnitrobenzene sulfonate are heated for 3 hours at165 to 166C, cooled to room temperature and poured into ice-water. Theprecipitate is suction filtered, washed 5 H 1 with water and dried. Theproduct obtained contains a H c-CH -CH -N-O S N O 0}; mixture of thedyes of the formulae:

and

H N 0 OH H C-N-O s 3 2 O OH 0 OH and dyes polyesterin full blue shades.The yield is 10.0 and dyes polyesters full blue shades. The yield isparts. parts.

The dyes set out in the following Table are obtained EXAMPLE 74 by amethod analogous to that described in Example 6: 10 parts of1,5-dihydroxy-4-(3-(N-nporpylsulfonamido)-anilino)-8-aminoanthraquinone,Z

50 parts of formamide and 4 parts of sodium l m-nitrobenzenesulfonateare heated for 3 hours at 165 to 167C, cooled to room temperature andpoured into ice-water. The precipitate is suction filtered, washed withwater and dried. H

The product obtained contains the dye of the formula: by starting fromthe appropriate aminoanthraquinones.

Example Y Z shade on polyester 75 -HN-SO NH(CH -CH -on blue 6 OH /CH3 7HN SO -NHCH CH 3 blue CH 77 OH mmgso nmcn bcm j blue 9; 78 -OH -HN--soNncn ecH on blue 79 -HN--SO NH(CH ocn -OH blue CH 80 -HN- -SO N 3 -OHblue CH CH OH CH CH 81 -HN- -SO N 2 3 -OH blue CH CH 82 -OH -HN--SO2N Hblue 85 -HN--SO2N b -OH blue 84 urnpfijwonncn -OH blue -ContinuedExample Y Z Shade on a. A polyester- 85 -OH -HN--CONHCH CH blue 86-HN--CONH(CH cH -OH blue 87 HN-@-CONH(CH OC H -OH blue 88' -HN--coml@-ou blue cu cu 89 -OH -uN--cou 3 blue 90 -HN-CON: H} -OH blue 91 -HN--COC H OH blue 92 -HN--CO (ca oc u OH blue 93 -NH--so -N@ -OH blue H 9-N-,-COO(CH -OC H -OH blue We claim: alkoxycarbonyl of a total of two tofive carbon 1. A dye of the formula: atoms, methyl, ethyl, methoxy orethoxy;

phenylthio;

alkanoylamino of two to six carbon atoms in which X N 'W one or twohydrogen atoms may be replaced by il chlorine, bromine, methyl, ethyl,methoxy or eth- Y/ oxy;

cycloalkanoylamino of seven to eight carbon atoms;

in which each of two of the radicals X is hydroxyl and the third X is aradical selected from the group consisting of:

alkylamino of one to eight carbon atoms in which one or two hydrogensmay be replaced by hydroxyl, alkoxy of one to three carbon atoms, cyano,carboxamido, N,N-dimethylcarboxamido, alkoxycarbonyl ofa total of two tofive carbon atoms, sulfonamido, N,N-dimethylsulfonamido or pyrrolidon-2-yl-l; phenylamino in which one or two hydrogens in the phenyl radicalmay be replaced by chlorine, bromine, hydroxyl, trifluoromethyl, nitro,sulfonamido or sulfonamido which is substituted on its nitrogen atom byalkyl of l to 8 carbon atoms or by alkoxyalkyl of 3 to 8 carbon atoms orwhich forms the amide with the nitrogen atom of piperidine orpyrrolidine or morpholine, carboxamido or N- alkylcarboxamido ofa totalof 2 to 7 carbon atoms,

benzoylamino in which one or two hydrogen atoms may be replaced bychlorine, bromine, methyl ethyl, methoxy or ethoxy; and

N'-alkylureido of two to five carbon atoms in the alkyl moiety.

2. A dye of the formula:

in which one X is hydroxyl and the other X is phenylamino in which oneor two hydrogens in the phenyl radical may be replaced by chlorine,bromine, trifluoromethyl, nitro, sulfonamido or sulfonamido which issubstituted on its nitrogen atom by alkyl of l to 8 carbon atoms or byalkoxyalkyl of 3 to 8 carbon atoms or which forms the amide with thenitrogen atom of piperidine or pyrrolidinc or morpholine, carboxamido orN- 6. The dye of the formula: zilkylcarboxamido ofa total of2 to 7carbon atoms, alkoxycarbonyl of a total of two to five carbon atoms,methyl, ethyl, methoxy or ethoxy.

3. A dye of the formula given in claim 2 in which one HO X is hydroxyland the other X is 3- sulfonamidophenylamino of the formula: 9 2 2 NHO Sin which R is hydrogen or alkyl of one to eight carbon atoms and Ris'hydrogen or alkoxyalkyl of three to The dye of the formula: eightcarbon atoms or l 3 G R H --S0 IS piperidme; pyrrohdme or morpholme. 2

4. The dye of the formula:

o 0 OH I 8. The dye of the formula: H NO S NH O OH HO Ill/TN 5. The dyeof the formula:

H N--SO o W G H l H NSO HO O OH UNITED STATES PATENT AND TRADEMARKOFFICE I CERTIFICATE OF CORRECTION PATENT No. 3,862,944

DATED January 28, 1975 NV ENTOR( 1 Heinz Eilingsfeld et 8.1

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In the Heading, insert --Foreign Application Priorit Date May 18, 1971Germany P 21 24 589. 6--

In Column 2, Lines 36 & 37, delete -chlorobutyrylamino" and substituteY-chlorobutyrylaminm- In Column 4, Line 24, delete (the 3-aminoanthraquinone..." and substitute (thed -aminoanthraquinone...--

In Column 4, Line 62, delete "...(2'-methylamilino)..." and substitute(2'-methylanilino).

In Column 7, Line 21, delete "washing it well. when an and substitute--washing it well. When an A Signed and Scaled this Seventeenth Day OfAugust 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uflarentsand Trademarks

2. A dye of the formula:
 3. A dye of the formula given in claim 2 inwhich one X'' is hydroxyl and the other X'' is 3-sulfonamidophenylaminoof the formula:
 4. The dye of the formula:
 5. The dye of the formula: 6.The dye of the formula:
 7. The dye of the formula:
 8. The dye of theformula: